CA1084520A - Polymerization and ring equilibration of trifluoroethyoxy-chloro-cyclotriphosphazenes - Google Patents
Polymerization and ring equilibration of trifluoroethyoxy-chloro-cyclotriphosphazenesInfo
- Publication number
- CA1084520A CA1084520A CA278,480A CA278480A CA1084520A CA 1084520 A CA1084520 A CA 1084520A CA 278480 A CA278480 A CA 278480A CA 1084520 A CA1084520 A CA 1084520A
- Authority
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- Canada
- Prior art keywords
- sodium
- compound
- reaction
- products produced
- chlorine atoms
- Prior art date
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- Expired
Links
- 238000006116 polymerization reaction Methods 0.000 title abstract description 8
- 238000011067 equilibration Methods 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- MSGMXYUAWZYTFC-UHFFFAOYSA-N sodium;2,2,2-trifluoroethanolate Chemical group [Na+].[O-]CC(F)(F)F MSGMXYUAWZYTFC-UHFFFAOYSA-N 0.000 claims description 6
- -1 sodium alkoxide Chemical class 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- NYYLKNDBZDKKAV-UHFFFAOYSA-N ClP1N=PN=P[N]1 Chemical class ClP1N=PN=P[N]1 NYYLKNDBZDKKAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 6
- 239000007795 chemical reaction product Substances 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical group [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims 2
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 150000007944 thiolates Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 9
- 125000004104 aryloxy group Chemical group 0.000 abstract description 6
- 125000001424 substituent group Chemical group 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- NXDBMYTZSNQBEW-UHFFFAOYSA-N 1,2,3,4-tetrahydro-1,3,5,2,4,6-triazatriphosphinine Chemical class N1=PNPNP1 NXDBMYTZSNQBEW-UHFFFAOYSA-N 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001212 derivatisation Methods 0.000 description 3
- 229920002627 poly(phosphazenes) Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 description 1
- COLOHWPRNRVWPI-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound [CH2]C(F)(F)F COLOHWPRNRVWPI-UHFFFAOYSA-N 0.000 description 1
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920002632 poly(dichlorophosphazene) polymer Polymers 0.000 description 1
- 229920003221 poly(phosphazene) elastomer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- RZWQDAUIUBVCDD-UHFFFAOYSA-M sodium;benzenethiolate Chemical compound [Na+].[S-]C1=CC=CC=C1 RZWQDAUIUBVCDD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Abstract The synthesis of phosphazene polymers and copolymers by a procedure in which up to three chlorine atoms in hexa-chlorocyclotriphosphazene are replaced with alkoxy or aryloxy groups and the resulting compounds are thermally polymerized to yield polymers with a desired distribution of substituents.
These may be further modified by replacement of the remaining chlorine atoms with other substituents.
Further the polymerization of mixtures containing polychlorocyclotriphosphazenes and various amounts of the cyclo-triphosphazenes in which some of the chlorine atoms have been replaced, is also described.
The products of said reaction are useful in the production of flame resistant foams, and are resistant to oil and other fluids.
These may be further modified by replacement of the remaining chlorine atoms with other substituents.
Further the polymerization of mixtures containing polychlorocyclotriphosphazenes and various amounts of the cyclo-triphosphazenes in which some of the chlorine atoms have been replaced, is also described.
The products of said reaction are useful in the production of flame resistant foams, and are resistant to oil and other fluids.
Description
: , POLYME~IZATION ~ND RI~IG E~,UILIBRATION ., ¦ OF TRIFLUOROETHOXY-C}~LORO-CVCLOTRIPHOSPHAZENES
. ~
¦ Specification This invention relates to phosphazene polymers~
. particularly those useful in the production of flame resistant : foam articles, or the production of poly(phosphazene) rubbers exhibiting ~lexibility at extremely low temperatures and those ,..
, 5 Possessing resistance to oils, fuels and other industrial ,, liquids.
Recently published"information concerning the produc-, tion of polytphosphaæenes) has described the preparation Or .' materials having molecular weights well in excess of 1,000,000 . 10 by a route which involves first the thermal po~ymerization o~
. hexachlorocyclotriphosphazene (NPC12)3 to yield a high molecuaar ;., weight linear polymer and subsequent replacement of the chlorine , atoms in the polymer with substituents selected to impart . desired prope:rties to the resulting poly(phosphazenes).
,, 15 Typical descriptions of these procedures wlll be ~ound ln the ~ollowin~ United States Patents:
3,370,020 Allcock et al issued ~ebruar,y 20, 1968, 3,515,688 Rose et al issued J'une 2, 1970, and 3,838,o73 Rose et al issued Septemher 24, 1974.
Another route described for the preparation of poly-(phosphazenes)involves an exchange Or llgands as described ln United States Patent 3,732,175 issued May 8, 1973.
None of t~e above disclosures permits the synthesis to be conducted in such a ~ashion that specific substituents ~5 on the phosphaæene polymer occupy selected and definite sites in the polymer.
~"
108~520 ¦ e present lnventlon 1s ad~ressed to the productlon of phosphazene polymers by a procedure ln which ~he hexachloro-cyclotriphosphazene is first reacted to e~fect repla~ement of up to three of the six chlorine atoms with a group such as an aryloxy (phenoxy) or alkoxy, e.g., a trifluoroethoxy gro~lp -OC~I2CF3 as a substituent on a specific P atom in the ring and preferably wlth a group which is ~oined to the P atom by an oxygen atom, e.g., alkoxy, aryloxy, etc., and subsequent thermal polymerlzation of the product which contains both Cl and tri-alkoxy or aryloxy ~roups and to the subsequent derivatization of such products with alkoxy, aryloxy or other groups to repla~e the remaining Cl atoms.
The thermal polymerization o~ fluoroalkoxychloro-cyclotriphosphazenes is described in a paper authored by V. N.
Prons, M. P. Grinblat and A. A. Klebanski published in Vysokomol Soyed A 16 No. 7 1620-1623 (1974) and reprinted in Polymer Science USSR Vol. 16, No. 6, A Series, pp. 1878~1~82 (1974).
According to the authors, those compounds with molar ratios of Cl~ -dihydroperfluoroalkoxy substituents of at least 2 (i.e.
Compounds I and II below) can be thermally polymerized to yield copolymers.
The prcsent lnvcntors have ~ound (l)"~hat ~hc coml~oun~
in whlch the mol ratio o~ Cl:trifluoroethoxy substituents is 1:1 can also be thermally polymerized to a copolymer and have further round (2) that the chlorine atoms remainlng in the copolymels obtained by thermal polymerization of polychlorocyclotriphospha-zenes in whlch 1, 2 or 3 of the chlorine atoms have been replaced with alkoxy or aryloxy groups prior to thermal polymerization . can be replaced wlth nucleophiles to yield poly(phosphazene) 3- I homo- and polymers.
i~45ZO
It has also been found thatpolychlorocyclotriphospha-zenes which result when 4, 5 or 6 of the chlorine atoms of the hexachlorocyclotriphosphazenes have been replaced with ~
dihydrofluoroalkoxy groups do not yield polymers when heated for long periods of time, i.e., that they are not thermally poly-merized in the same way as hexachlorocyclotriphosphazenes in which only 1, 2 or 3 of the chlorine atoms have been replaced.
For the products formed when hexachlorocyclotriphos-phazenes reacted with sodium trifluoroethoxide, several possible structures exlst depending on how many chlorine atoms in the hexachlorocyclotriphosphazene are replaced by fluoroalkoxy group. The following are possible structures which result:
¦ p~ p~
¦¦ Cl~ !~ 1 Cl\¦ ~CCU2CF3 Cl ~N/\Cl Cl/~/ bCl 1 replaced 2 replaced . (I) (II) .. ~ CF3cH20\ ~OCH2cF3 1~ \~ N \ I
CF3CH2O\ ~ ¦/0CH2CF3 C1~ ¦ OCH2CF3 Cl/ ~N ~Cl CF3CK20 9~ ~Cl 3 rep:Laced ~4 replaced (III) (IV) CF3CH20~,~0CH2cF3 CF3CH2\ ~CH2C 3 N~ N N~ N
¦¦ CF3CH 2y Jf CU 2cF3 CF3CU 2C~ OCH 2CF3 ,~ . 2 3 CF3CH2N OCH2GF3 . 5 replaced . 6 replaced (V) (VI ) ~.~8~5~Z
It has been found that each of Compounds I, II
; and III polymerize at a specific temperature between about 200C and 250C, and that the resulting polymers can be derivatized, e.g. by treatment with sodium trifluoroethoxide in anhydrous tetrahydrofuran, producing film forming, color-less materials useful as coatings and similar to the de-rivatized materials described in Allcock United States Patent 3,370,020 issued February 20, 1968. The molecular weights of all three derivatized polymers (determined by gel permeation chromatography) were found to be in the range of 100,000 to 400,000. The reduced specific viscosities were in the range of 0.2 to 0.3. The yields of polymer from the three trimers were in the range of 33~ (from I), 68% (from II), and 85~ (from III). It will be seen that the poly-merization of III is much more complete than the polymeriza-tion of either I or II.
At 200 C Compounds I and II polymerized during 4 hours to yield colorless, gum-like materials. 'rhe other timers were unreactive at this temperature. The polymers obtained from I and II were derivatized by further treatment with sodium trifluoroethoxide to yield colorless, film-forming materials. These were similar to the higher molecular weight polymers obtained by treatment of poly (dichlorophosphazene) with sodium trifluoroethoxide as described in the above noted prior art. Compound III which did not polymerize at 200C, polymerized when heated at ~ - 6 --1~84520 225C for 48 hours. However Compounds IV, V and VI yielded no open chain polymers even when heated at temperatures of 275C or 300C for extended periods of time.
lQ
.
; 6a - ~ .
', ' ' - ~
,, ~ , .
: As previously indicated, a furtller aspect Or this invention is the derivatization o~ the copolymers produced by thermal polymerization o~ the chlorocyclotriphosphazene compounds identified as I, II and II~, above, either by reaction of the - 5 thermally produced copolymer with sodium tri~luoroethoxide asdescribed above, or by reaction o~ the copolymers resulting ~rom the thermal polymerization o~ any o~ Compounds I~ II or III with some other suitable compounds which react by replacing the chlorine atoms present in the copolymer. Suitable compounds include (1) other sodium fluoroalkoxides, particularly dihydro~luoroalkoxides; (2) sodium aryloxldes, including sodium phenoxide and sodium phenoxldes which are substituted with one or more halogen or alkyl (Cl-C9) groups, including linear and branched alkyl groups; (3) primary and secondary amines such as dimethylamine or other alkylamines; and (4) sodium thioIates such as sodium thiophenolate. Other compGunds Or a similar nature, which react with the chlorine atoms pre-sent in the copolymers o~ Compounds I, II and III may be used ln place o~ the named compounds.
Sultable primary and secondary amines ~or reaction with the chlorine atoms may be represented by the general rormulac RNll2 and n2NII in which R is a linear, branchcd or cyclo aliphatic group with up to 10 carbons or in which R is a heterocyclic ring such as morpholine, 2,6-dimethyl`morpholine or plperidine, etc. Also compounds in which R is an aromatic ring such as phenyl, naphthyl, etc.
, .
~nother aspect Or the present inventioll is the copolymerization o~ rnixtures Or (NPC12)3 and any o~ Compounds I through VI and especially with [NPtOCH2CF3)2]3 in which the latter compounds are present in an amount sufficient to signi-ficantly affect the course of the polymerization. For example, it has been found that at 200~C mixtures contalning from 10 mol %
to 50 mol % of [~P(OCH2CF3)3]3 in (NPC12)3 yielded elastomeric pol~meric pr~ducts. The copolymer obtained from a mixture Or 5 ol Z ~NP(ocH2cF3)2]3 in (NPC12)3 was soluble in ethyl acetate, methyl ethyl ketone, or tetrahydrofuran (THF) and exhi~
bited an intrinsic viscosity of 0.4 dl/g in the latter solvent.
Microanalysis indicated a composition corresponding to ~ 40%
residues ~rom ~NP(OCH2CF3)2]3 and 60% from (NPC12)3. Derivati-zation of this product with piperidine yielded a polymer which (by microanalysis) contained ~ 40% NP(OCII2CF3)2 and 60%
NP(I~CsH10)2 residues. The intrinsic viscosity in TH~ was 0.71 dl/g, and the Mn value (by osmometry) was 110,000. The infra-red spectrum WclS conslstent with an open chain polymer structure.
Polymerization o~ the (NPC12)3~NP(OCH2CF3)2]3 place at a lower temperature than is required for the polymeri l;
zation of (NPC12)3 alone indicative of a different mechanistic pn~hway ~or ~he copolyrnerizatlons ~han for thc homopolymerl-zation of (NPC12)3.
The results of polymerizlng mlxtures with various proportions of (NPcl2)3 and ~NP(0CH2CF3)2]3 in the mixture are shown in Table I.
.
:: , .
.
i~845~0 ¦ Lowering of tile relative amount Or ~NP(OC~I2CF3)2~3 in the initial mlxture lowered the proportion Or these residues in the polymer. A polymer which appeared to be almost exclu-¦ sively tNPC12)n was formed at 200 when the ratio of' (NPC12)3 ¦ to [NP(OCH2CF3)2~3 was 90:10. From these results it appears that [NP(0CI~2CF3)2]3 is an accelerator for the linear polymeri-zation of (NPC12)3. On the other hand, (NPC12)3 is not a cata-lyst for the polymerization Or CNP(OCH2C~3)2]3, since no poly-mers were obtained from mixtures which contained a high propor-on of ~NP(0CH2CF3)2~3 and a low proportion of (NPC12)3.
However, tNPC12)3 appears to accelerate the ring expans.lon r~actiOns of [NP(ocH2cF3)2]n-Direct analysis of the polymerizate by 31p nmr spectroscopy confirmed that roughly equimolar amounts of NPC12 and NP(0CH2CF3)2 residues were present in polymers prepared from equimolar amounts of the two trimers. Althou~h phospha-zene cyclic oligomers could be detected in the polymers, the oligomers could be removed by solvent extraction. Moreover, treatment of the polymer with sodium trirluoroethoxide ylelded a s~ecies with a 31p nmr spectrum iden~ical to that of an authentic sample o~ ~NP(0CH2CF3)2]n prepared ~rorn pure (NPC12)n.
Ilencc, lt was concluded that graft copolymers, ~cncrated ~y the ; grafting of cyclic trimeric rings on to a linear chaln, are not formed under these reaction conditions.
Typical results for various mixtures of (NPC12)3 and ~NPt0CH2CF3)2]3 maintained at 200C ~or the indicated number of days are given in Table I below.
_9 .
- .
- ~; lOl-DZO ,L,, I
I ~ o ~,n ~
. I ~ ~
I O
¦ , h a~ h C) O ~ o O C~ ~ C,> ~ Z
h h C~ ~ h '-- bP~ o l . ~1 ~ ~ ~ ~o b~ ~ o ~ h l ~ ~ ~ 1 ~ C~ E~
¦ ~ h I i I I I I I H ~1 ¦ t~l F. Il I ~1 ~1 0 U~ 0 C~ ,, W
Z: ~ ~Z; C) I I ,~
. ~ ~ ~ O~ O~
~ N ~D ~ I I I I . I
H N
Cq :I: ~) 3 o ~ h a) ~-- ~ F~ c) ~ ~ ~ ~ .
H X _` O IJ~ h r--l , ~ ~:~ C~oll J~ .
a: P~ ~ ~ ~ ~0- ~ 'e~
¢ O ~1 1~ N
E-~ ~ :~ ~_~/ . ,~
. _ . o~) ~JV .
H N ~ ~ . . .
~ C~ Co ~ I I . . ' ~ :Z
~: ~ .
1 ~ ~ ~ 0 ~ 3 O~ N
~ C) ~rl ~ N N ~t U~ N ~ 3 ~J N
O ~ ~ ~ , .J 3 L
. ', h xl 0 a~ 0~ ~ ~I r-l 0 .. ~ o~ - - . .- .. .. ..
; . ~0 r~ ~ O ~ t_ o~ o X~
U~ O o O O
. ~ O 3 ::t N t-- o Ir~ O -1 . ~1 ~ N ~ J ~1 o ~X . .
~,_ V~ O ~ O O O O N
. H I N ~ O L~ O C~ ~D
~0 X O ~ .
, -10-. ~
~1- lO~g5ZO
T~BLF I , (Continued) . ' a. At 200 b. Time re~uired to reach immobilization of the mixture at 200 (except ~or the 0:100~ 1:99, 10:90, 99:1 and 100:0 molar mixtures which were ~luid when the reaction times were terminated).
c. A ~ sign means that the compound was detected, but its relative concentration was not measured.
d. Based on 31p nmr analysis.
e . No NP( H2CF3) 2 residues could be deteooed by 31p nmr , `
.
. ', I
'.' ~' .
. ~
¦ Specification This invention relates to phosphazene polymers~
. particularly those useful in the production of flame resistant : foam articles, or the production of poly(phosphazene) rubbers exhibiting ~lexibility at extremely low temperatures and those ,..
, 5 Possessing resistance to oils, fuels and other industrial ,, liquids.
Recently published"information concerning the produc-, tion of polytphosphaæenes) has described the preparation Or .' materials having molecular weights well in excess of 1,000,000 . 10 by a route which involves first the thermal po~ymerization o~
. hexachlorocyclotriphosphazene (NPC12)3 to yield a high molecuaar ;., weight linear polymer and subsequent replacement of the chlorine , atoms in the polymer with substituents selected to impart . desired prope:rties to the resulting poly(phosphazenes).
,, 15 Typical descriptions of these procedures wlll be ~ound ln the ~ollowin~ United States Patents:
3,370,020 Allcock et al issued ~ebruar,y 20, 1968, 3,515,688 Rose et al issued J'une 2, 1970, and 3,838,o73 Rose et al issued Septemher 24, 1974.
Another route described for the preparation of poly-(phosphazenes)involves an exchange Or llgands as described ln United States Patent 3,732,175 issued May 8, 1973.
None of t~e above disclosures permits the synthesis to be conducted in such a ~ashion that specific substituents ~5 on the phosphaæene polymer occupy selected and definite sites in the polymer.
~"
108~520 ¦ e present lnventlon 1s ad~ressed to the productlon of phosphazene polymers by a procedure ln which ~he hexachloro-cyclotriphosphazene is first reacted to e~fect repla~ement of up to three of the six chlorine atoms with a group such as an aryloxy (phenoxy) or alkoxy, e.g., a trifluoroethoxy gro~lp -OC~I2CF3 as a substituent on a specific P atom in the ring and preferably wlth a group which is ~oined to the P atom by an oxygen atom, e.g., alkoxy, aryloxy, etc., and subsequent thermal polymerlzation of the product which contains both Cl and tri-alkoxy or aryloxy ~roups and to the subsequent derivatization of such products with alkoxy, aryloxy or other groups to repla~e the remaining Cl atoms.
The thermal polymerization o~ fluoroalkoxychloro-cyclotriphosphazenes is described in a paper authored by V. N.
Prons, M. P. Grinblat and A. A. Klebanski published in Vysokomol Soyed A 16 No. 7 1620-1623 (1974) and reprinted in Polymer Science USSR Vol. 16, No. 6, A Series, pp. 1878~1~82 (1974).
According to the authors, those compounds with molar ratios of Cl~ -dihydroperfluoroalkoxy substituents of at least 2 (i.e.
Compounds I and II below) can be thermally polymerized to yield copolymers.
The prcsent lnvcntors have ~ound (l)"~hat ~hc coml~oun~
in whlch the mol ratio o~ Cl:trifluoroethoxy substituents is 1:1 can also be thermally polymerized to a copolymer and have further round (2) that the chlorine atoms remainlng in the copolymels obtained by thermal polymerization of polychlorocyclotriphospha-zenes in whlch 1, 2 or 3 of the chlorine atoms have been replaced with alkoxy or aryloxy groups prior to thermal polymerization . can be replaced wlth nucleophiles to yield poly(phosphazene) 3- I homo- and polymers.
i~45ZO
It has also been found thatpolychlorocyclotriphospha-zenes which result when 4, 5 or 6 of the chlorine atoms of the hexachlorocyclotriphosphazenes have been replaced with ~
dihydrofluoroalkoxy groups do not yield polymers when heated for long periods of time, i.e., that they are not thermally poly-merized in the same way as hexachlorocyclotriphosphazenes in which only 1, 2 or 3 of the chlorine atoms have been replaced.
For the products formed when hexachlorocyclotriphos-phazenes reacted with sodium trifluoroethoxide, several possible structures exlst depending on how many chlorine atoms in the hexachlorocyclotriphosphazene are replaced by fluoroalkoxy group. The following are possible structures which result:
¦ p~ p~
¦¦ Cl~ !~ 1 Cl\¦ ~CCU2CF3 Cl ~N/\Cl Cl/~/ bCl 1 replaced 2 replaced . (I) (II) .. ~ CF3cH20\ ~OCH2cF3 1~ \~ N \ I
CF3CH2O\ ~ ¦/0CH2CF3 C1~ ¦ OCH2CF3 Cl/ ~N ~Cl CF3CK20 9~ ~Cl 3 rep:Laced ~4 replaced (III) (IV) CF3CH20~,~0CH2cF3 CF3CH2\ ~CH2C 3 N~ N N~ N
¦¦ CF3CH 2y Jf CU 2cF3 CF3CU 2C~ OCH 2CF3 ,~ . 2 3 CF3CH2N OCH2GF3 . 5 replaced . 6 replaced (V) (VI ) ~.~8~5~Z
It has been found that each of Compounds I, II
; and III polymerize at a specific temperature between about 200C and 250C, and that the resulting polymers can be derivatized, e.g. by treatment with sodium trifluoroethoxide in anhydrous tetrahydrofuran, producing film forming, color-less materials useful as coatings and similar to the de-rivatized materials described in Allcock United States Patent 3,370,020 issued February 20, 1968. The molecular weights of all three derivatized polymers (determined by gel permeation chromatography) were found to be in the range of 100,000 to 400,000. The reduced specific viscosities were in the range of 0.2 to 0.3. The yields of polymer from the three trimers were in the range of 33~ (from I), 68% (from II), and 85~ (from III). It will be seen that the poly-merization of III is much more complete than the polymeriza-tion of either I or II.
At 200 C Compounds I and II polymerized during 4 hours to yield colorless, gum-like materials. 'rhe other timers were unreactive at this temperature. The polymers obtained from I and II were derivatized by further treatment with sodium trifluoroethoxide to yield colorless, film-forming materials. These were similar to the higher molecular weight polymers obtained by treatment of poly (dichlorophosphazene) with sodium trifluoroethoxide as described in the above noted prior art. Compound III which did not polymerize at 200C, polymerized when heated at ~ - 6 --1~84520 225C for 48 hours. However Compounds IV, V and VI yielded no open chain polymers even when heated at temperatures of 275C or 300C for extended periods of time.
lQ
.
; 6a - ~ .
', ' ' - ~
,, ~ , .
: As previously indicated, a furtller aspect Or this invention is the derivatization o~ the copolymers produced by thermal polymerization o~ the chlorocyclotriphosphazene compounds identified as I, II and II~, above, either by reaction of the - 5 thermally produced copolymer with sodium tri~luoroethoxide asdescribed above, or by reaction o~ the copolymers resulting ~rom the thermal polymerization o~ any o~ Compounds I~ II or III with some other suitable compounds which react by replacing the chlorine atoms present in the copolymer. Suitable compounds include (1) other sodium fluoroalkoxides, particularly dihydro~luoroalkoxides; (2) sodium aryloxldes, including sodium phenoxide and sodium phenoxldes which are substituted with one or more halogen or alkyl (Cl-C9) groups, including linear and branched alkyl groups; (3) primary and secondary amines such as dimethylamine or other alkylamines; and (4) sodium thioIates such as sodium thiophenolate. Other compGunds Or a similar nature, which react with the chlorine atoms pre-sent in the copolymers o~ Compounds I, II and III may be used ln place o~ the named compounds.
Sultable primary and secondary amines ~or reaction with the chlorine atoms may be represented by the general rormulac RNll2 and n2NII in which R is a linear, branchcd or cyclo aliphatic group with up to 10 carbons or in which R is a heterocyclic ring such as morpholine, 2,6-dimethyl`morpholine or plperidine, etc. Also compounds in which R is an aromatic ring such as phenyl, naphthyl, etc.
, .
~nother aspect Or the present inventioll is the copolymerization o~ rnixtures Or (NPC12)3 and any o~ Compounds I through VI and especially with [NPtOCH2CF3)2]3 in which the latter compounds are present in an amount sufficient to signi-ficantly affect the course of the polymerization. For example, it has been found that at 200~C mixtures contalning from 10 mol %
to 50 mol % of [~P(OCH2CF3)3]3 in (NPC12)3 yielded elastomeric pol~meric pr~ducts. The copolymer obtained from a mixture Or 5 ol Z ~NP(ocH2cF3)2]3 in (NPC12)3 was soluble in ethyl acetate, methyl ethyl ketone, or tetrahydrofuran (THF) and exhi~
bited an intrinsic viscosity of 0.4 dl/g in the latter solvent.
Microanalysis indicated a composition corresponding to ~ 40%
residues ~rom ~NP(OCH2CF3)2]3 and 60% from (NPC12)3. Derivati-zation of this product with piperidine yielded a polymer which (by microanalysis) contained ~ 40% NP(OCII2CF3)2 and 60%
NP(I~CsH10)2 residues. The intrinsic viscosity in TH~ was 0.71 dl/g, and the Mn value (by osmometry) was 110,000. The infra-red spectrum WclS conslstent with an open chain polymer structure.
Polymerization o~ the (NPC12)3~NP(OCH2CF3)2]3 place at a lower temperature than is required for the polymeri l;
zation of (NPC12)3 alone indicative of a different mechanistic pn~hway ~or ~he copolyrnerizatlons ~han for thc homopolymerl-zation of (NPC12)3.
The results of polymerizlng mlxtures with various proportions of (NPcl2)3 and ~NP(0CH2CF3)2]3 in the mixture are shown in Table I.
.
:: , .
.
i~845~0 ¦ Lowering of tile relative amount Or ~NP(OC~I2CF3)2~3 in the initial mlxture lowered the proportion Or these residues in the polymer. A polymer which appeared to be almost exclu-¦ sively tNPC12)n was formed at 200 when the ratio of' (NPC12)3 ¦ to [NP(OCH2CF3)2~3 was 90:10. From these results it appears that [NP(0CI~2CF3)2]3 is an accelerator for the linear polymeri-zation of (NPC12)3. On the other hand, (NPC12)3 is not a cata-lyst for the polymerization Or CNP(OCH2C~3)2]3, since no poly-mers were obtained from mixtures which contained a high propor-on of ~NP(0CH2CF3)2~3 and a low proportion of (NPC12)3.
However, tNPC12)3 appears to accelerate the ring expans.lon r~actiOns of [NP(ocH2cF3)2]n-Direct analysis of the polymerizate by 31p nmr spectroscopy confirmed that roughly equimolar amounts of NPC12 and NP(0CH2CF3)2 residues were present in polymers prepared from equimolar amounts of the two trimers. Althou~h phospha-zene cyclic oligomers could be detected in the polymers, the oligomers could be removed by solvent extraction. Moreover, treatment of the polymer with sodium trirluoroethoxide ylelded a s~ecies with a 31p nmr spectrum iden~ical to that of an authentic sample o~ ~NP(0CH2CF3)2]n prepared ~rorn pure (NPC12)n.
Ilencc, lt was concluded that graft copolymers, ~cncrated ~y the ; grafting of cyclic trimeric rings on to a linear chaln, are not formed under these reaction conditions.
Typical results for various mixtures of (NPC12)3 and ~NPt0CH2CF3)2]3 maintained at 200C ~or the indicated number of days are given in Table I below.
_9 .
- .
- ~; lOl-DZO ,L,, I
I ~ o ~,n ~
. I ~ ~
I O
¦ , h a~ h C) O ~ o O C~ ~ C,> ~ Z
h h C~ ~ h '-- bP~ o l . ~1 ~ ~ ~ ~o b~ ~ o ~ h l ~ ~ ~ 1 ~ C~ E~
¦ ~ h I i I I I I I H ~1 ¦ t~l F. Il I ~1 ~1 0 U~ 0 C~ ,, W
Z: ~ ~Z; C) I I ,~
. ~ ~ ~ O~ O~
~ N ~D ~ I I I I . I
H N
Cq :I: ~) 3 o ~ h a) ~-- ~ F~ c) ~ ~ ~ ~ .
H X _` O IJ~ h r--l , ~ ~:~ C~oll J~ .
a: P~ ~ ~ ~ ~0- ~ 'e~
¢ O ~1 1~ N
E-~ ~ :~ ~_~/ . ,~
. _ . o~) ~JV .
H N ~ ~ . . .
~ C~ Co ~ I I . . ' ~ :Z
~: ~ .
1 ~ ~ ~ 0 ~ 3 O~ N
~ C) ~rl ~ N N ~t U~ N ~ 3 ~J N
O ~ ~ ~ , .J 3 L
. ', h xl 0 a~ 0~ ~ ~I r-l 0 .. ~ o~ - - . .- .. .. ..
; . ~0 r~ ~ O ~ t_ o~ o X~
U~ O o O O
. ~ O 3 ::t N t-- o Ir~ O -1 . ~1 ~ N ~ J ~1 o ~X . .
~,_ V~ O ~ O O O O N
. H I N ~ O L~ O C~ ~D
~0 X O ~ .
, -10-. ~
~1- lO~g5ZO
T~BLF I , (Continued) . ' a. At 200 b. Time re~uired to reach immobilization of the mixture at 200 (except ~or the 0:100~ 1:99, 10:90, 99:1 and 100:0 molar mixtures which were ~luid when the reaction times were terminated).
c. A ~ sign means that the compound was detected, but its relative concentration was not measured.
d. Based on 31p nmr analysis.
e . No NP( H2CF3) 2 residues could be deteooed by 31p nmr , `
.
. ', I
'.' ~' .
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of producing phosphazene polymers with molecular weights between 1 x 103 and 1 x 107 which comprises;
(1) replacing up to three chlorine atoms of hexa-chlorocyclotriphosphazene (NPCl2)3 by reaction with a sodium alkoxide or aryloxide;
(2) recovering the resulting substituted chloro-cyclotriphosphazene reaction product;
(3) maintaining said reaction product at a tempera-ture between 200°C and 250°C for a time sufficient to thermally polymerize said reaction product to a substituted chlorophos-phazene copolymer; and (4) recovering said copolymer.
(1) replacing up to three chlorine atoms of hexa-chlorocyclotriphosphazene (NPCl2)3 by reaction with a sodium alkoxide or aryloxide;
(2) recovering the resulting substituted chloro-cyclotriphosphazene reaction product;
(3) maintaining said reaction product at a tempera-ture between 200°C and 250°C for a time sufficient to thermally polymerize said reaction product to a substituted chlorophos-phazene copolymer; and (4) recovering said copolymer.
2. The process of Claim 1 in which three of the chlorine atoms of said hexachlorocyclotriphosphazene are replaced in said reaction with a sodium alkoxide or aryloxide.
3. The process of Claim 2 in which said reaction is between said hexachlorocyclotriphosphazene and a sodium .alpha.,.alpha.-dihydroperfluoroalkoxide with up to 12 carbon atoms in the alkoxy group.
4. The process of Claim 3 in which said alkoxide is sodium trifluoroethoxide.
5. The process of Claim 1 including in addition the step of derivatizing said recovered copolymer by reaction with a compound which replaces the chlorine atoms present in said copolymer.
6. The process of Claim 5 in which said compound is a sodium fluoroalkoxide.
7. The process of Claim 6 in which said compound is sodium trifluoroethoxide.
8. The process of Claim 5 in which said compound is a sodium aryloxide.
9. The process of Claim 8 in which said aryloxide is a phenoxide or a phenoxide substituted with at least one halogen atom, or an alkyl group with up to 9 carbon atoms.
10. The process of Claim 5 in which said compound is a primary or secondary amine.
11. The process Or Claim 10 in which said amine is a dimethyl amine.
12. The process of Claim 5 in which said compound is a sodium thiolate.
13. The process of Claim 12 in which said thiolate is sodium thhiophenolate.
14. The products produced by the process of Claim 2.
15. The products produced by the process of Claim 5.
16. The products produced by the process of Claim 7.
17. The products produced by the process of Claim 9.
18. The products produced by the process of Claim 11.
19. The products produced by the process of Claim 13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68706976A | 1976-05-17 | 1976-05-17 | |
| US687,069 | 1984-12-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084520A true CA1084520A (en) | 1980-08-26 |
Family
ID=24758918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA278,480A Expired CA1084520A (en) | 1976-05-17 | 1977-05-16 | Polymerization and ring equilibration of trifluoroethyoxy-chloro-cyclotriphosphazenes |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS534100A (en) |
| AU (1) | AU511328B2 (en) |
| BE (1) | BE854757A (en) |
| CA (1) | CA1084520A (en) |
| DE (2) | DE2759712C2 (en) |
| GB (1) | GB1543544A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574676A (en) * | 2020-05-21 | 2020-08-25 | 上海工程技术大学 | Flame-retardant aqueous polyurethane emulsion |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS584017Y2 (en) * | 1977-11-04 | 1983-01-24 | シャープ株式会社 | liquid fuel combustion equipment |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3370020A (en) | 1964-09-29 | 1968-02-20 | American Cyanamid Co | Process for the production of phosphonitrilic polymers and polymers produced thereby |
| US3515688A (en) | 1967-08-30 | 1970-06-02 | Horizons Research Inc | Extreme service phosphonitrile elastomers |
| US3732175A (en) * | 1971-09-27 | 1973-05-08 | Firestone Tire & Rubber Co | Crosslinking of phosphazene polymers |
| JPS4912570A (en) * | 1972-05-15 | 1974-02-04 | ||
| SE374377B (en) * | 1972-07-17 | 1975-03-03 | Mo Och Domsjoe Ab | |
| US3836608A (en) * | 1972-08-17 | 1974-09-17 | Fmc Corp | Process for self condensing phosphonitrilic chloroesters and product |
| US3838073A (en) * | 1972-08-28 | 1974-09-24 | Horizons Research Inc | Poly(fluoroalkoxyphosphazene)homopolymers |
| CA1028339A (en) * | 1973-06-12 | 1978-03-21 | Carroll W. Lanier | Process for producing phosphazene fire retardant |
-
1977
- 1977-05-13 DE DE2759712A patent/DE2759712C2/de not_active Expired - Lifetime
- 1977-05-13 DE DE2721826A patent/DE2721826A1/en active Granted
- 1977-05-16 AU AU25156/77A patent/AU511328B2/en not_active Expired
- 1977-05-16 CA CA278,480A patent/CA1084520A/en not_active Expired
- 1977-05-16 JP JP5625077A patent/JPS534100A/en active Granted
- 1977-05-17 BE BE177681A patent/BE854757A/en not_active IP Right Cessation
- 1977-05-17 GB GB20682/77A patent/GB1543544A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574676A (en) * | 2020-05-21 | 2020-08-25 | 上海工程技术大学 | Flame-retardant aqueous polyurethane emulsion |
| CN111574676B (en) * | 2020-05-21 | 2022-02-08 | 上海工程技术大学 | Preparation method of flame-retardant waterborne polyurethane emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2721826A1 (en) | 1977-12-08 |
| GB1543544A (en) | 1979-04-04 |
| JPS534100A (en) | 1978-01-14 |
| BE854757A (en) | 1977-11-17 |
| JPS5432840B2 (en) | 1979-10-17 |
| AU511328B2 (en) | 1980-08-14 |
| DE2721826C2 (en) | 1987-10-22 |
| AU2515677A (en) | 1978-11-23 |
| DE2759712C2 (en) | 1990-01-11 |
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